Potentially harmful metals, and health risk evaluation in groundwater of Mardan, Pakistan: Application of geostatistical approach and geographic information system

Abstract This study investigates the values of pH, total dissolved solids (TDS), elevation, oxidative reduction potential (ORP), temperature, and depth, while the concentrations of Br, and potentially harmful metals (PHMs) such as Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe in the groundwater samples. Moreover, geographic information system (GIS), XLSTAT, and IBM SPSS Statistics 20 software were used for spatial distribution modeling, principal component analysis (PCA), cluster analysis (CA), and Quantile-Quantile (Q-Q) plotting to determine groundwater pollution sources, similarity index, and normal distribution reference line for the selected parameters. The mean values of pH, TDS, elevation, ORP, temperature, depth, and Br were 7.2, 322 mg/L, 364 m, 188 mV, 29.6 °C, 70 m, 0.20 mg/L, and PHMs like Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe were 0.38, 0.26, 0.08, 0.27, 0.36, 0.22, 0.04, 0.43 and 0.86 mg/L, respectively. PHMs including Cr (89%), Cd (43%), Mn (23%), Pb (79%), Co (20%), and Fe (91%) exceeded the guideline values set by the world health organization (WHO). The significant R2 values of PCA for selected parameters were also determined (0.62, 0.67, 0.78, 0.73, 0.60, 0.87, −0.50, 0.69, 0.70, 0.74, −0.50, 0.70, 0.67, 0.79, 0.59, and −0.55, respectively). PCA revealed three geochemical processes such as geogenic, anthropogenic, and reducing conditions. The mineral phases of Cd(OH)2, Fe(OH)3, FeOOH, Mn3O4, Fe2O3, MnOOH, Pb(OH)2, Mn(OH)2, MnO2, and Zn(OH)2 (−3.7, 3.75, 9.7, −5.8, 8.9, −3.6, 2.2, −4.6, −7.7, −0.9, and 0.003, respectively) showed super-saturation and under-saturation conditions. Health risk assessment (HRA) values for PHMs were also calculated and the values of hazard quotient (HQ), and hazard indices (HI) for the entire study area were increased in the following order: Cd>Ni>Cu>Pb>Mn>Zn>Cr. Relatively higher HQ and HI values of Ni, Cd, Pb, and Cu were greater than one showing unsuitability of groundwater for domestic, agriculture, and drinking purposes. The long-term ingestion of groundwater could also cause severe health concerns such as kidney, brain dysfunction, liver, stomach problems, and even cancer.